Oxidation of acetone

A modern reagent, that has found increased application, is dimethyldioxirane it is prepared in situ by oxidation of acetone with potassium peroxomonosul-fate KHSOs. ... 

The oxidation of lactate ion by alkaline permanganate (0.1 M base) was examined as part of the general study of the oxidation of acetone and its possible oxidation products . The reaetion is first-order in lactate ion, and, if it is assumed that it is also first-order in oxidant, then the second-order rate coefficient is 2 l.mole sec" at 25 °C. 

A mixture of equal parts of nitric acid, acetone and 75% acetic acid, used to etch nickel, will explode 1.5-6 h after mixing if kept in a closed bottle. The presence of the diluted acetic acid would probably slow the known violent oxidation of acetone by nitric acid [1] (but would not prevent slow oxidation with gas evolution). Alternatively, the formation of tetranitromethane and subsequent oxidation of acetone was postulated [2], but this is perhaps unlikely, because presence of acetic anhydride is normally necessary for formation of tetranitromethane. 

Accidental addition of a little acetone to the residue from wet-ashing a polymer with mixed nitric-sulfuric acids and hydrogen peroxide caused a violent explosion [1]. The peroxoacid would be produced under these conditions, and is known to react with acetone to produce the explosive acetone peroxide [2], but direct oxidation of acetone may have been responsible. 

Nef prepared acetol in several ways, the more important of which depended upon the reaction between bromoacetone and potassium or sodium formate or acetate, and the subsequent hydrolysis of the ester by methyl alcohol.1 2 Acetol is also formed, together with pyruvic acid, by the direct oxidation of acetone by Baeyer and Villiger s acetone-peroxide reagent.3... 

Other photocatalytic reactions that have been successfully investigated by in situ solid-state NMR spectroscopy are the oxidation of 2-propanol (197) and the oxidation of acetone (198). 

In this regard, it is well to remember the role which the wall plays on the nature of the products obtained from gas phase oxidation. There is certainly common agreement that walls and wall reactions are important in this respect. For example, Hay et al. (11) have shown the importance of the walls in determining the nature and composition of the oxygenated products from 2-butane + 02 at 270°C. Cohens study on the photo-oxidation of acetone also illustrates this point (10). He found that if acetone is photolyzed by itself in a quartz vessel, the normal products—methane, ethane, carbon monoxide, and methyl ethyl ketone— are produced. 

The rather toxic methylglyoxal is formed in many organisms and within human tissues.174 It arises in part as a side reaction of triose phosphate isomerase (Eq. 13-28) and also from oxidation of acetone (Eq. 17-7) or aminoacetone, a metabolite of threonine (Chapter 24).175 In addition, yeast and some bacteria, including E. coli, have a methylglyoxal synthase that converts dihydroxyacetone to methylglyoxal, apparently using a mechanism similar to that of triose phosphate isomerase. It presumably forms enediolate 2 of Eq. 13-26, which eliminates inorganic phosphate to yield methyl-... 

The acetone-oxone system of Curci can be used for epoxidation of a,p-unsat-urated acids if NaHC03 is present as a buffer to prevent Baeyer-Villiger oxidation of acetone yields are in the range 60-92% (4 examples).2... 

The properties of O-, in contrast to these of the conjugated acid HO, are still poorly studied. The review by J. Lee and Grabowsky (1992) describes mass spectrometry of this radical. In conditions that are usual for synthetic organic chemistry, O- displays less reactivity than its acid OH. Oxidation of acetone by radicals O and OH leads to quite different products (Morkovnik Orhlobystin 1979) see combined Scheme 1-83 ... 

W.Y. Choi, J.Y. Ko, H.W. Park, J.S. Chung, Investigation on TiC>2 -coated optical fibers for gas-phase photocatalytic oxidation of acetone, Appl. Catal. B Environ. 31 (2001) 209-220. 

Zorn ME, Tompkins DT, Zeltner WA, Anderson MA. Photocatalytic oxidation of acetone vapor on Ti02/Zr02 thin films. Appl Catal B Environ 1999 23 1-8. 

The chain oxidation of acetone presumably takes place chiefly, then, according to reaction (35) [or (39) and (40) ] followed by (20) and... 

Reactions involving abstraction from acetaldehyde are just as likely in diethyl ketone oxidation as reactions involving abstraction from formaldehyde in acetone oxidation. The acetyl radical so produced will oxidize as in the oxidation of acetone to give mostly carbon dioxide (from the -carbon atom of diethyl ketone71), but a little decomposition seems to occur since some carbon monoxide does not come from the original carbonyl group of the ketone.71... 

We have found it useful to prepare authentic samples of the various diperoxides encountered by using a variation of the Baeyer-Villiger oxidation conditions. Oxidation of ketones at low temperatures using peracetic acid has been reported (23) to give diperoxides instead of the esters produced under Baeyer-Villiger conditions. Authentic samples of 10 and 11, can be prepared, respectively, by the peracetic oxidation of acetone and methyl ethyl ketone jointly or methyl ethyl ketone alone. We are studying the mechanism of this interesting oxidation reaction. 

Choi W, Ko JY, Park H, Chung JS (2001) Investigation on Ti02-coated Optical Fibers for Gas-phase Photocatalytic Oxidation of Acetone, Appl. Catal. B Environ. 31 209-220. 

The photo-oxidation of acetone [51], methyl ethyl ketone [52] and diethyl ketone [53, 54] at temperatures between 100 and 250 °C has yielded some further information on these reactions and Hoare and... 

Dimethyldioxirane (DMDO) is a mild reagent for epoxidation under neutral conditions of electron-rich as well as of electron-deficient alkenes.Moreover, dimethyldioxirane is often the oxidant of choice for the preparation of labile epoxides. The reagent is prepared by oxidation of acetone with potassium caroate KHSO5 (Oxone) and is stable in acetone solution at —20 °C for several days. ... 

As a general example we may examine the oxidation of acetone. Formic and acetic acids can be formed according to the equation (CH3)2C0(Z) + 02( ) ->HC00H(Z) + CH3C00H(Z), for which the standard affinity is 139,300 cal. 

R = OH). Although similar oxidation of acetone-palmatine gives an 8,13a-propanoberberine analogous to (119 R = OH, R = H), 13-methyl-acetone-berberine (115 R = Me) gives mainly the lactam (121) together with small amounts... 

Tsuboi, T. Ishii, K. Tamura, S., Themal oxidation of acetone behind reflected shock wave, in Proceedings of the 17th International Colloquium on the Synamics of Explosions and Reactive Systems, Heidelberg, Germany, July 25-30, 1990... 

The vinoxy CH2CHO and 1-methylvinoxy (acetonyl) radicals are key intermediates in the mechanisms of many reactions of importance for atmospheric and combustion chemistry. The formation of vinoxy radicals has been observed in several chemical processes. They may be formed in reactions of OH radicals with ethylene oxide (C2H4O) and with acetylene (C2H2) in the presence of 02.8 They are also produced in reactions of 0(3P) atoms with alkenes and in the reactions of reactive atoms such as F or 0(3P) with acetaldehyde.164,165 The 1-methylvinoxy (acetonyl) radical CH2C(CH3)0 is considered an important intermediate in the atmospheric oxidation of acetone initiated by the OH radical.166171 Spectroscopic studies by Washida et al.164 and Williams et al.m allow estimation of the rate constant for the reaction of acetonyl with 02. 

Preparation. The reagent can be prepared in 70-90% yield by oxidation of acetone hydrazone with yellow mercuric oxide (British Drug Houses) catalyzed by potassium hydroxide. In the absence of base the hydrazone is not oxidized by mercuric oxide.1 Unstable solutions are obtained by use of silver oxide in place of mercuric oxide.2... 

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